Coating composition with accelerated low temperature cure

ABSTRACT

A coating composition including an unsaturated resin selected from polyesters, alkyds or combinations thereof; an alkoxy (meth)acrylic functional monomer, and a thermoplastic compound containing active hydrogen groups; a curing agent; and a curing promoter such as at least one metal drier.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.11/879,021, filed July 13, 2007, now U.S. Pat. No. 7,951,856, which isincorporated herein by reference.

TECHNICAL FIELD

The present disclosure relates to coating compositions that are suitablefor use in formulating stains, primers, sealers and topcoats to finish awide variety of substrates (e.g. wood, plastic and metal).

BACKGROUND

Traditional industrial protective coatings based on urea/melamineformaldehyde resin crosslinked systems have good performance and costefficiency. However, coatings that release formaldehyde during cure arecurrently disfavored by customers. Alternative coating chemistries, suchas isocyanates or azridine crosslinked systems, may have health orsafety issues and typically have higher raw material costs thanurea/formaldehyde resin systems. Other alternative coating chemistries,such as epoxies or silane compounds, are also expensive and typicallymust be cured at a relatively high temperature. Yet other alternativecoating chemistries, such as organic peroxide cured unsaturatedpolyester coating systems that include styrene, are also currentlydisfavored by customers for health and safety reasons. Without styrene,the peroxide cured polyester coating systems generally require highercuring temperatures and/or extended curing times that are not suitablefor many commercial applications.

SUMMARY

In general, the present disclosure is directed to coating compositionswith cure conditions and raw material costs similar to or better thanthose for conventional urea/melamine formaldehyde resin crosslinkedcoating systems. These coating compositions cure without strong colordevelopment, which makes them well suited to formulate stains, primers,sealers and topcoats to finish a wide variety of substrates (e.g. wood,plastic and metal). In preferred embodiments, the coating compositionsare at least substantially free of any of formaldehyde, isocyanate andstyrene.

In one aspect, the present disclosure is directed to a coatingcomposition including an unsaturated resin selected from polyesters,alkyds or combinations thereof; an alkoxy (meth)acrylic functionalmonomer; a thermoplastic compound containing active hydrogen groups; acuring agent; and a curing promoter such as at least one metal drier.

In yet another aspect, the present disclosure is directed to a method ofmaking a coating composition, including reacting the followingcomponents to form a coating composition: (1) a first component A,including about 20 wt % to about 90 wt %, based on the total weight ofthe composition, of an unsaturated polyester resin, about 1 wt % toabout 50 wt % of: an alkoxy (meth)acrylic functional monomer, and athermoplastic compound containing active hydrogen groups; and about 0.1wt % to about 3 wt % of least one metal drier; and (2) a secondcomponent B, including about 0.5 wt % to about 5 wt % of at least oneorganic peroxide.

In yet another aspect, the present disclosure is directed to a methodincluding (1) providing a coating composition including an unsaturatedpolyester resin, an alkoxy (meth)acrylic functional monomer, and athermoplastic compound containing active hydrogen groups reactive underfree radical initiated curing; at least one metal drier, and a peroxide;and (2)applying the coating composition to a substrate.

In yet another aspect, the present disclosure is directed to a substratehaving applied thereon a cured coating composition. The coatingcomposition includes an unsaturated polyester resin; an alkoxy(meth)acrylic functional monomer, and a thermoplastic compoundcontaining active hydrogen groups reactive under free radical initiatedcuring; at least one metal drier; and a peroxide.

The details of one or more embodiments of the invention are set forth inthe description below. Other features, objects, and advantages of theinvention will be apparent from the description, and from the claims.

DETAILED DESCRIPTION

In one embodiment, the coating composition includes at least one of anunsaturated polyester resin, an alkyd resin or combinations thereof; atleast one an alkoxy (meth)acrylic functional monomer and a thermoplasticcompound containing active hydrogen groups; a curing agent, and a curingpromoter such as a metal drier.

A wide variety of unsaturated polyester and alkyd resins may be used inthe coating composition. Any functionalized polyester or alkyd resinwith ethylenic units may be used. Unsaturated polyesters and alkyds withhydroxyl, carboxyl, or allyl ether functionality are suitable, andunsaturated polyester resins and alkyds with allyl ether functionalityare preferred. Preferred unsaturated polyesters and alkyds have a weightaverage molecular weight of about 500 to about 10,000, preferably about1000 to about 6000, and more preferably about 2000 to about 5000.

Unsaturated polyester resins are preferred, and suitable examplesinclude, but are not limited to, those available under the tradedesignation Roskydal from Bayer AG, Pittsburgh, Pa., and Roskydal 502BAis particularly preferred.

The unsaturated resin is typically present at about 10 wt % to about 80wt %, preferably at about 20 wt % to about 60 wt %, and more preferablyat about 30 wt % to about 50 wt %, based on the total weight of thecoating composition.

The coating composition further includes at least one alkoxy(meth)acrylic functional monomer and a thermoplastic compound.

Suitable alkoxy (meth)acrylic functional monomers include: (1) at leastone pendant (meth)acrylic functional group positioned at a terminal endand/or along a backbone; and (2) at least one alkoxy (OR, wherein R isany alkyl radical) linking group along the backbone. In thisapplication, (meth)acrylic and the designation Ac refer to an acrylategroup, a methacrylate group, or mixtures and combinations thereof

Preferred alkoxy (meth)acrylic functional monomers have a molecularweight of about 200 to about 2000, and include multiple (meth)acrylicfunctional groups and at least one alkoxy group along the backbone. Morepreferred alkoxy (meth)acrylic functional monomers include di andtri(meth)acrylic functional compounds with at least one alkoxy groupalong the backbone. The alkoxy group is preferably an ethylene oxide ora propylene oxide group. Most preferably, the backbone includes about 8to about 16, preferably about 8 to about 12, and more preferably about8, ethoxy or propoxy repeat units, and ethoxy repeat units areparticularly preferred.

For example, a particularly preferred monomer may have the formula[Ac—O—R₁—(OR₂)_(n)—R₁—O—Ac], where R₁ and R₂, or both, can be (CH₂)_(x),with x=2, and n=8 to 12.

Suitable alkoxy (meth)acrylic functional monomers include, but are notlimited to, polyethylene glycol or polypropylene glycoldi(meth)acrylates available from Sartomer Corp., Exton, Pa., under thetrade designations Sartomer SR 209, 210, 252, 259, 268, 344, 603, 610,644, 740, and/or combinations thereof.

The alkoxy (meth)acrylic functional monomers are typically present atabout 0.5 wt % to about 50 wt %, preferably at about 1 wt % to about 30wt %, and more preferably at about 3 wt % to about 10 wt %, based on thetotal weight of the coating composition.

Substitution is anticipated on the organic groups used in the coatingcompositions of the present invention. Thus, when the term “group” isused to describe a chemical substituent, the described chemical materialincludes the unsubstituted group and that group with O, N, Si, or Satoms, for example, in the chain (as in an alkoxy group) as well ascarbonyl groups or other conventional substitution. For example, thephrase “alkyl group” is intended to include not only pure open chainsaturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl,t-butyl, and the like, but also alkyl substituents bearing furthersubstituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl,halogen atoms, cyano, nitro, amino, carboxyl, etc. Thus, “alkyl group”includes ether groups, haloalkyls, nitroalkyls, carboxyalkyls,hydroxyalkyls, sulfoalkyls, etc.

In addition to the alkoxy (meth)acrylic functional monomers, the coatingcomposition further includes a thermoplastic polymer with activehydrogen groups that are reactive under free radical initiated curing.Suitable thermoplastic polymers include thermoplastic co-promotercompounds that, according to presently available evidence, acceleratethe curing reactions and improve at least one property of the uncured orcured coating such as, for example, sagging resistance and flexibility.The thermoplastic compound may include any synthetic resin with activehydrogen groups. Suitable examples include cellulose based resins andacetoxy or acetate functionalized acrylics which are obtained throughfree radical polymerization of ethylenic monomers. Preferred examplesinclude, but are not limited to, cellulose or cellulose derivatizedresins such as cellulose acetate butyrate (CAB), cellulose acetate (CA)and combinations thereof

The thermoplastic compounds are typically present in the coatingcomposition at about up to about 20 wt %, preferably about 0.2 wt % toabout 20 wt %, more preferably about 0.5 wt % to about 10 wt %, and mostpreferably from about 0.5 wt % to about 6 wt %, based on the totalweight of the coating composition.

The coating composition also preferably includes at least one curingagent. A wide range of curing agents may be used, and peroxidecompounds, particularly organic peroxides, are particularly preferred.Examples of organic peroxides include ketone peroxides, peresters,perketals, and benzoyl peroxides such as those available under the tradedesignation Luperox from Arkema, Philadelphia, Pa. Ketone peroxides arepreferred, and suitable ketone peroxides are available under the tradename Luperox from Arkema, Inc., as well as from Norac, Inc., Azusa,Calif., under the trade designation Norox. Norox MEKP-9, which is asolution of methyl ethyl ketone (MEK) peroxide in dimethyl phthalate, isparticularly preferred.

The curing agent is typically present in the coating composition atabout 0.2 wt % to about 5 wt %, preferably about 0.5 wt % to about 3 wt%, and more preferably about 0.5 wt % to about 2.0 wt %, based on thetotal weight of the coating composition.

The coating composition further includes at least one metal drier toenhance curing speed. Suitable metal driers include metal salts oforganic acids effective in catalyzing free-radical polymerization of theunsaturated polyester used in the coating composition. Metal driers aretypically metal salts of cycloalkanic acids such as naphthenic acid,alkanic acids such as neodecanoic acids, and C8 to C20 fatty acids.Suitable metals include Co, Mn, Pb, Ce, Zr, Ca, Zn, Bi, Cu, Cr, Li, K,Ni, Ne and mixtures and combinations thereof. Preferred metal driersinclude napthenates and C8 to C20 fatty acid salts of K, Co, Mg, Ca andmixtures and combinations thereof. Particularly preferred metal driersinclude Co salts, and include, for example, cobalt naphthalates,citrate, acetyl-acetonate, 2-ethylhexanoate, and the like. Metal driersin an organic hydrocarbon solvent are preferred for use in the coatingcomposition. Suitable commercially available metal driers include, forexample, those available from Tenneco, Inc., Piscataway, N.J. under thetrade designation Syn Nuxtra Co 12, Syn Nuxtra Mg 12, and Syn Nuxtra K15.

The metal driers may be present in the coating composition in anycatalytically effective amount, and typically the driers are present atabout 0.1 wt % to about 2 wt %, preferably about 0.2 wt % to about 2 wt%, and more preferably about 0.3 wt % to about 1.5 wt %, based on thetotal weight of the coating composition.

The coating composition is preferably solvent borne. Suitable organicsolvents include, but are not limited to, butyl acetate, methyl ethylketone (MEK), xylene and mixtures and combinations thereof

The organic solvent is preferably present in the coating composition atabout 5 wt % to about 80 wt %, preferably about 5 wt % to about 70 wt %,and more preferably about 5 wt % to about 60 wt %, based on the totalweight of the coating composition.

Additional (meth)acrylic functional monomers may optionally beincorporated into the coating composition to improve and/or modify theproperties of the cured coating. Suitable (meth)acrylic functionalmonomers preferably include multiple (meth)acrylate functional groups,which may be positioned at the terminal ends and/or along the backboneof the monomer.

In one embodiment, the optional (meth)acrylic functional monomersinclude, but are not limited to, di(meth)acrylates having the formulaAc—(Z)_(n)—Ac, wherein Z is preferably alkoxy and n=1 to 5. In anotherembodiment, the (meth)acrylic functional compounds include, but are notlimited to, tri(meth)acrylates with the formula Ac—[Z(Ac)₂]_(n), whereinZ is preferably alkoxy and n=1 to 8. The alkoxy group Z in the di andtri (meth)acrylate compounds may include a linear or branched alkylradical, which may be substituted or unsubstituted. Unsubstituted linearalkyl groups with less than about 5 carbon atoms are preferred.

Suitable examples include tripropylene glycol diacrylates such as thoseavailable from Sartomer Corp., Exton, Pa, under the trade designationSartomer SR 306, as well as trimethylolpropopane triacrylates such as,for example, those available from Sartomer under the trade designationSartomer SR 351, as well as combinations thereof.

The acrylic functional monomers are typically present in the coatingcomposition at about 0 wt % to about 50 wt %, preferably about 2 wt % toabout 20 wt %, and more preferably at about 2 wt % to about 10 wt %,based on the total weight of the coating composition.

The coating composition further optionally includes at least one surfaceactive agent to enhance the flow/leveling and/or wetting properties ofthe coating composition. Suitable surface active agents include, but arenot limited to, silicones and polyacrylates such as those availableunder the trade designation Byk from Byk-Chemie, Wesel, Germany.Suitable compounds include Byk 333, Byk 348, Byk 353, Byk 380 andmixtures and combinations thereof

The surface active agent, if present, is included in the coatingcomposition at about 0.1 wt % to about 3 wt %, preferably about 0.1 wt %to about 2 wt %, and more preferably about 0.1 wt % to about 1 wt %,based on the total weight of the coating composition.

The coating composition further optionally includes at least onerheology control agent to control sagging and pigment settling of thewetting properties of the coating composition. Suitable rheology controlagents include, but are not limited to, polyureas such as thoseavailable under the trade designation Byk from Byk-Chemie, Wesel,Germany. Suitable compounds include Byk 410, 411 and mixtures andcombinations thereof

The rheology control agent, if present, is included in the coatingcomposition at about 0.1 wt % to about 3 wt %, preferably about 0.1 wt %to about 2 wt %, and more preferably about 0.1 wt % to about 1 wt %,based on the total weight of the coating composition.

The coating composition may also optionally include solid particles suchas pigments, fillers, matting agents, colorants, wax, and the like.Pigments are preferably used to give the coating composition therequired hiding and opacity upon drying and curing. In addition tocolorants, pigments may also be used to incorporate a desired color tothe substrate, for example, white pigment may be used to form a coatingcomposition having a white color. Alternatively, or in concert withhaving a desired color, flatting agents such as silicas may be used togive the substrate a desired matte finish. Suitable solid particles inthis invention are present in the amount sufficient to give the desiredopacity, finish texture, and/or general aesthetic quality to the coatedsubstrate. Suitable pigments include aluminum oxides, titanium oxides,zinc oxides, and the like. An example of a pigment usable in thepresently described coating composition includes Ti-Pure R-900,available from E. I. duPont de Nemours of Wilmington, Del.; Suitableflatting agents include, for example, amorphous silica (silica oxides)such as those available under the trade designation Syloid 169 from W.R. Grace Company of Baltimore, Md. Suitable fillers include, forexample, clays, talc or other inorganic compounds. An example of afiller usable in the presently described coating composition includesMinex 10, available from Unimin Specialty Minerals Inc.

The amount of solid particles used in the coating composition may varywidely depending on the intended finish. For example, the amount ofsolid particles used is preferably less than about 40 wt % of thecoating composition.

The unsaturated resin, the alkoxy acrylic functional monomers and thethermoplastic compounds, the curing agent, a catalytically effectiveamount of at least one metal drier, and any optional additives may bemixed in an organic solvent to form a coating composition. Preferably, afirst component, referred to herein as component A, and a secondcomponent referred to herein as component B, are mixed to form thecoating composition. For example, component A, which is preferablysolvent-borne, may include an unsaturated resin, the alkoxy(meth)acrylic functional monomer and the thermoplastic compound, themetal drier and any optional additives. Component B includes the curingagent.

The coating composition can be formulated into a stain, a primer, asealer, a topcoat and the like to finish wood, engineered wood, plasticand metal substrates. Since the coating composition is rapidly curableat low temperatures, it is particularly well suited for application towood substrates, and typical applications include home and/or officefurniture, kitchen cabinets, flooring, window frames, doors, siding andthe like.

The coating composition may be applied to a substrate by anyconventional method, including, for example, spraying, brushing, dipcoating, sheet coating, coil coating, roll coating, and the like. Aspray system including a two component gun with equalizers has beenfound to provide particularly consistent results.

Following application, the coating composition is cured to form aprotective and/or decorative coating on the substrate. The cure timevaries depending on the cure conditions selected, such as temperature,dwell time, room temperature, and the like. If desired, the coatedsubstrate may be heated, for example, in a conventional oven. While notwishing to be bound by any theory, presently available data indicatethat alkoxy linking groups in the (meth)acrylic functional monomer orthermoplastic resin that has active hydrogen groups reactive to freeradicals enhance the curing reactions of the unsaturated polyestercompound and promote the film formation, which reduces cure times at lowtemperatures and provides a coating with low color development.

The coating composition may then be cured at low temperatures, which inthis application refers to temperatures less than 70° C., to form acoating on the substrate. At room temperature, the coating compositioncures in less than about 24 hours. At more preferred curing temperaturesof about 30° C. to about 60° C., the coating composition cures in lessthan about 30 minutes, more preferably less than about 20 minutes. At acuring temperature of about 30° C. to about 60° C., the coatingcomposition cures to form a coating in about 5 minutes to about 30minutes, more preferably in about 5 minutes to about 20 minutes, andeven more preferably in about 6 minutes to about 15 minutes.

In certain embodiments, the coating composition and coating aresubstantially free of formaldehyde, isocyanates and styrene. Inpreferred embodiments the coating composition and coating areessentially free of formaldehyde, isocyanates and styrene, morepreferably essentially completely free of formaldehyde, isocyanates andstyrene, and most preferably completely free of formaldehyde,isocyanates and styrene.

The term substantially free means that the coating compositions andcoating are contaminated with, or liberate as a result of curing, nomore than about 0.5 percent by weight of any of formaldehyde, isocyanateand styrene. The term essentially free means that the coatingcompositions and coating are contaminated with, or liberate as a resultof curing, no more than about 0.5 percent by weight of any offormaldehyde, isocyanate and styrene. The term essentially completelyfree means that the coating compositions and coating are contaminatedwith, or liberate as a result of curing, no more than about 0.1 percentby weight of any of formaldehyde, isocyanate and styrene. The termcompletely free means that the coating compositions and coatings arecontaminated with, or liberate as a result of curing, less than 5 partsper million (ppm) of any of formaldehyde, isocyanate and styrene.

In a preferred embodiment, following cure the coating on the substrateis not substantially tinted, and in a preferred embodiment forms asubstantially colorless film. In some embodiments the cured coatingforms a water white, no color film. The color of a sample may beevaluated by any known technique based on the CIE L*a*b* color scheme.For example, to evaluate the color of a sample a spectrophotometer suchas those available from Datacolor, Inc under the trade designationSpectraflash, Model No. SF650X, may be used.

The cured coating is also highly flexible, which ensures that it willnot crack, chip or delaminate from a substrate, particularly on edges orcomplex contours. The flexibility of the coating was tested usingPentagon Mandrel Rods according to ASTMD 522-80 and the results weregraded on a scale of 1 to 10, in which 10 indicates the most flexiblecoating, and 1 indicates the least flexible coating.

EXAMPLES

In a 2000 ml stainless steel beaker, 1000 grams of each of the coatingformulations was prepared for testing. The first component A wasformulated and the ingredients were accurately weighted and added intothe beaker in the order gradually under agitation (10-15 RPM) accordingto Table 1. In Table 1, compositions 6-7 exemplify preferred coatingcompositions, while compositions C1-C2 denote comparative examples.

Each sample was filtered (10 micro filter bags) and stored in a linedmetal can for testing after a complete homogeneous formulation wasachieved. 97 grams of each component A was weighed into a lined metalcan (250 ml) and 3 grams of component B was dropwise added underagitation. The mixed sample was drawn down on white Leneta Charts usinga 3 mil bird applicator within 5 minutes and the coated charts were airflash dried at room temperature for 15 minutes before placing the chartsin an oven at 50° C. as function of the curing time. The curing time wasrecorded after the coating surface became tack-free for fingers in alatex glove.

The color reading of the cured coating compositions on the white LenentaCharts was measured using a Spectraflash SF650X from Datacolor(Lawrenceville, N.J.) against the standard white background. Theflexibility of the cured coating compositions was determined at a roomtemperature using Pentagon Mandrel Rods according to ASTMD 522-80 andthe results were graded on a scale of 1 to 10, in which 10 indicates themost flexible coating, and 1 indicates the least flexible coating. Theproperties of the resulting coating compositions are shown in Table 2.

TABLE 1 Coating Compositions Components Composition C1 C2 1 2 3 4 5 6 7Component A Roskydal 502 BA 400 400 400 400 400 400 400 400 400Trimethylolpropane 90 90 90 90 90 90 90 90 70 Triacrylate Tripropyleneglycol 60 60 0 0 0 60 60 0 0 diacrylate Polyethylene glycol 0 0 60 0 0 00 60 70 diacrylates (400) Polyethylene glycol 0 0 0 60 0 0 0 0 0dimethacrylates (400) Polypropylene glycol 0 0 0 0 60 0 0 0 0dimethacrylate (400) Cellulose acetate 0 0 0 0 0 30 0 30 40 butyratePolyacrylics, Paralloid 0 0 0 0 0 0 30 0 0 B-66 Syn Nuxtra Cobalt 12 6.09.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 Syn Nuxtra Mg 12 2.0 4.0 2.0 2.0 2.0 2.02.0 2.0 2.0 Syn Nuxtra K 15 2.0 5.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Byk 3804.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Byk 348 4.0 4.0 4.0 4.0 4.0 4.0 4.04.0 4.0 Byk 353 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Butyl acetate 230222 230 230 230 230 230 230 230 MEK 160 160 160 160 160 160 160 160 160Xylene 10 10 10 10 10 10 10 10 10 Component B Norox ® MEKP-9 30 30 30 3030 30 30 30 30 Total 1000 1000 1000 1000 1000 1000 1000 1000 1000

TABLE 2 Properties of the Coating Compositions Curing Time Formulas(min) Color, dE Flexibility * Formula C1 28 4.12 5 Formula C2 20 7.18 3Formula 1 23 3.88 7 Formula 2 24 3.88 7 Formula 3 28 3.91 5 Formula 4 254.22 6 Formula 5 27 4.31 5 Formula 6 19 4.08 7 Formula 7 17 4.16 8

In comparison with control C1, compositions 6 and 7 with additions ofpolyethylene glycol diacrylate showed significantly faster curing speedand less curing time, less color change and improved flexibility.

Addition of more metal driers speeded the curing of the coatingformulation and decreased the curing time (Composition C2). However, theuse of more metal driers resulted in strong color development, which isless desired for aesthetic reasons, especially on light or whitesubstrates.

The addition of cellulose acetate butyrate (CAB) in examples 4, 6 and 7increased the curing reaction in comparison with addition of non-activehydrogen containing polyacrylics Paralloid B66 (Example 5) and controlcomposition C1. Compositions with addition of both polyethylene glycolacrylate and cellulose acetate butyrate (Compositions 6 and 7) showedthe fastest curing speed, good flexibility and low color developmentrelative to composition C2.

Various embodiments of the invention have been described. These andother embodiments are within the scope of the following claims.

1. A method of making a coating composition, comprising reacting thefollowing components to form a coating composition: (1) a firstcomponent A, comprising: about 20 wt % to about 90 wt %, based on thetotal weight of the composition, of an unsaturated polyester resin,wherein the unsaturated polyester comprises allyl ether functionality,about 1 wt % to about 50 wt % of: an alkoxy (meth)acrylic functionalmonomer, wherein the functional monomer is selected from di andtri(meth)acrylic functional compounds with about 8 to about 16 ethoxy orpropoxy groups along a backbone and a thermoplastic compound containingactive hydrogen groups, wherein the thermoplastic compound is selectedfrom cellulose resins and cellulose derivatized resins; and about 0.1 wt% to about 3 wt % of least one metal drier, wherein the metal drier is ametal salt of an organic acid, and wherein the metal comprises Co, Mn,Pb, Ce, Zr, Ca, Zn, Bi, Cu, Cr, Li, K, Ni, Mg and mixtures andcombinations thereof, and (2) a second component B, comprising about 0.5wt % to about 5 wt % of at least one organic peroxide; wherein thecoating composition is substantially free of any of formaldehyde,isocyanate and styrene.
 2. The method of claim 1, wherein component Afurther comprises about 5 wt % to about 80 wt % of at least one organicsolvent.
 3. The method of claim 1, wherein component A further comprisesup to about 50 wt % of at least one second (meth)acrylic functionalmonomer.
 4. The method of claim 1, wherein the metal comprises K, Co, Mgand mixtures and combinations thereof.
 5. The method of claim 1, whereinthe metal driers comprise Co.
 6. The method of claim 1, wherein thecoating composition further comprises about 0.2 wt % to about 20 wt % ofthe thermoplastic compound.
 7. The method of claim 1, wherein thethermoplastic compound is selected from cellulose acetate butyrate(CAB), cellulose acetate (CA) and combinations thereof.
 8. The method ofclaim 1, wherein the thermoplastic compound is cellulose acetatebutyrate (CAB).
 9. The method of claim 1, wherein the coatingcomposition further comprises about 0.1 wt % to about 3 wt % of at leastone surface active agent.
 10. A method, comprising: (1) providing acoating composition comprising: an unsaturated polyester resincomprising allyl ether functionality, an alkoxy (meth)acrylic functionalmonomer, wherein the functional monomer is selected from di andtri(meth)acrylic functional compounds with about 8 to about 16 ethoxy orpropoxy groups along a backbone, and a thermoplastic compound containingactive hydrogen groups reactive under free radical initiated curing,wherein the thermoplastic compound is selected from cellulose acetatebutyrate (CAB), cellulose acetate (CA) and combinations thereof; atleast one metal drier, wherein the metal drier is a metal salt of anorganic acid, and a peroxide, wherein the coating composition issubstantially free of any of formaldehyde, isocyanate and styrene; and(2) applying the coating composition to a substrate.
 11. The method ofclaim 10, further comprising curing the coating composition to form acured coating.
 12. The method of claim 11, wherein the coatingcomposition is cured at room temperature for less than about 24 hours.13. The method of claim 11, wherein the coating composition is cured ata temperature of about 30° C. to about 60° C. for about 30 minutes toabout 60 minutes.
 14. The method of claim 11, wherein the coatingcomposition is cured at a temperature of about 50° C. to about 60° C.for less than about 20 minutes.
 15. The method of claim 10, wherein thecoating composition is applied by spraying.
 16. The method of claim 14,wherein the coating composition is applied by spraying with a twocomponent gun system.
 17. A substrate having applied thereon a curedcoating composition, wherein the coating composition comprises anunsaturated polyester resin comprising allyl ether functionality; analkoxy (meth)acrylic functional monomer, wherein the functional monomeris selected from di and tri(meth)acrylic functional compounds with about8 to about 16 ethoxy or propoxy groups along a backbone, and athermoplastic compound containing active hydrogen groups reactive underfree radical initiated curing, wherein the thermoplastic compound isselected from cellulose acetate butyrate (CAB), cellulose acetate (CA)and combinations thereof; at least one metal drier, wherein the metaldrier is a metal salt of an organic acid; and a peroxide; wherein thecoating composition is substantially free of any of formaldehyde,isocyanate and styrene.